3-fuoropyridyl-2-oxy-phenoxy derivatives having herbicidal activity

ABSTRACT

There are described novel 3-fluoropyridyl-2-oxy derivatives having a herbicidal action and an action reducing the growth of grasses, which compounds correspond to the formula I ##STR1## wherein X is halogen or the trifluoromethyl group, and 
     Z is an alkanoic acid derivative which is more precisely described in the specification. 
     These compounds are suitable for the selective control of weeds in crops of cultivated plants, or for the reduction of the growth of grasses.

This is a divisional of application Ser. No. 844,407 filed on Mar. 26,1986, now U.S. Pat. No. 4,740,235.

In the published European Patent Application EP-A-83 556, there havealready been described 3-fluoropyridyl-2-oxyphenoxy derivatives havinghericidal activity, which correspond to the formula ##STR2## wherein Qis oxygen or sulfur, R is, inter alia, hydrogen, a metal or ammoniumion, or an unsubstituted or substituted c₁ -C₉ -alkyl, C₃ -C₉-cycloalkyl, C₃ -C_(9-alkenyl) or C₃ -C₉ -alkynyl group, or a C₃ -C₉-cycloalkenyl group or an imino group, and X is chlorine, bromine oriodine.

These compounds exhibited a good selective-herbicidal action inparticular against gramineous weeds in crops of cultivated plants, suchas cereals, maize, rice, cotton, soya bean and sugar beet.

It has been shown that a further group of novel3-fluoropyridyl-2-oxy-phenoxy derivatives have an excellentselective-herbicidal action, both in the pre-emergence andpost-emergence process, against in particular gramineous weeds in cropsof cultivated plants.

The novel 3-fluoropyridyl-2-oxy-phenoxy derivatives correspond to theformula I ##STR3## wherein X is a halogen atom or the trifluoromethylgroup, and

Z is an alkanecarboxylic acid radical --CH(CH₃)Z¹, CH₂ Z², --CH(C₂H₅)Z², --CH(CH₂ OCH₃)Z² or --CH₂ --CZ³ ═CH₂, in which

Z¹ is a radical --COQ--(CR¹ R²)_(n) --(CR³ R⁴)_(m) --Y¹, --CONA¹ A²,--CONA¹ (OA²), --COQCHA³ --COOA⁴, --C(OA⁵)═NA⁶, --COC(COA⁷)═CA⁸ (OA⁹),--COOCA⁸ ═CA⁹ --COA⁷, --CSQR, --COQ--G--Y², --CO--PO(OR¹⁴)O_(P) R¹⁵,--COQ--G--A¹⁰, --COQ--G--A¹¹, and --COQ--G--A¹²,

Z² is a radical --COQR or is the same as Z¹,

m is zero, 1 or 2,

n is 1 or 2,

Z³ is a radical --COOA⁹ or --CN,

Y¹ is a radical --CH(OR¹⁶)₂, a benzoyl, benzylsulfonyl, benzylsulfinyl,naphthoyl or phenyl-C₁ -C₄ -alkylcarbonyl radical, which is substitutedin the phenyl ring by R⁷ and R⁸, or is a radical --NR¹⁰ R¹¹ or --NR¹²COQ¹ R¹³,

Y² is a radical --OPQ² (OR¹⁴)₂, --PO(OR¹⁴)(O)_(P) R¹⁵ or --SiA⁷ (O_(P)R¹²)R¹³,

Q, Q¹, Q² independently of one another are each oxygen or sulfur,

R is hydrogen or the equivalent of an alkali metal, alkaline-earthmetal, copper or iron ion, or is a quaternary C₁ -C₄ -alkylammonium orC₁ -C₄ -hydroxyalkylammonium radical, C₁ -C₉ -alkyl, straight-chain orbranched-chain, unsubstituted or substituted by halogen, hydroxyl,cyano, nitro, phenyl, C₁ -C₄ -alkoxy(C₁ -C₄ -alkoxy)_(q) or a radical--COOR⁵, --COSR⁵, --CON(R⁵)₂, --NR⁵ R⁶ or -NR⁵ R⁹ R⁶⊕ M.sup.⊖, or is C₃-C₉ -cycloalkyl, an unsaturated aliphatic or alicyclic radical which cancontain N and which contains 2-9 C atom and at least one double ortriple bond, or is phenyl, unsubstituted or substituted by halogen, C₁-C₄ -alkyl, C₁ -C₄ -alkoxy, CN, COCH₃ or a radical --COOR⁵, --COSR⁵ or--CONR⁵ R⁶,

R¹, R², R³, R⁴ independently of one another are each hydrogen, C₁ -C₆-alkyl or phenyl,

R⁵ is hydrogen, C₁ -C₆ -alkyl, C₁ -C₆ -haloalkyl, C₂ -C₈ -alkoxyalkyl,C₃ -C₆ -alkenyl, C₃ -C₆ -haloalkenyl or C₃ -C₆ -alkynyl,

R⁶ is the same as R⁵, or is a phenyl or benzyl radical which isunsubstituted or substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,CN, NO₂, COCH₃, --COOR⁵, --COSR⁵ or --CON(R⁵)₂,

R⁷, R⁸ independently of one another are each hydrogen, C₁ -C₄ -alkyl, C₁-C₄ -alkoxy, halogen, CF₃, NO₂, CN, --CO--(C₁ -C₄ -alkyl) or --COO(C₁-C₄ -alkyl),

R⁹ is the same as R⁵ but is independent thereof,

R¹⁰, R¹¹ together are C₂ -C₅ -alkylene radicals, which form togetherwith the nitrogen atom to which they are linked a saturated 5- or6-membered heterocycle, which can additionally contain an oxygen orsulfur atom or a group --NR¹²,

R¹², R¹³ are each C₁ -C₆ -alkyl,

R¹⁴, R¹⁵ independently of one another are each hydrogen, C₁ -C₄ -alkyl,C₃ -C₄ -alkenyl, C₃ -C₄ -alkynyl, C₂ -C₄ -haloalkyl, C₁ -C₄ -alkoxy-(C₂-C₄)-alkyl, C₁ -C₄ -cyanoalkyl, or a phenyl, phenyl-(C₁ -C₄)-alkyl ornaphthyl radical, which is unsubstituted or mono- or disubstituted byhalogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄-haloalkoxy, nitro or cyano, where p is 0 or 1, and q is 0 or a numberfrom 1-4, and R¹⁵ is not H when p is 0,

R¹⁶ is C₁ -C₄ -alkyl, or the two radicals R¹⁶ together form abranched-chain or straight-chain C₂ -C₈ -alkylene chain,

M is the anion of an organic or inorganic acid,

A¹, A² are the same as R⁵ or R⁶ but are independent thereof, or C₂ -C₆-alkenyl groups which together with the nitrogen atom form a saturated5- or 6-membered heterocyclic ring,

A³, A⁴ are C₁ -C₄ -alkylene groups, which together with the CHCOO groupform a 5- or 6-membered lactone,

A⁵, A⁶ are C₁ -C₄ -alkylene groups, which together with the grouping towhich they are linked form an unsaturated heterocyclic ring,

A⁷ is C₁ -C₆ -alkyl or C₁ -C₆ -alkoxy,

A⁸ is hydrogen or C₁ -C₆ -alkyl,

A⁷ and A⁸ are a C₁ -C₆ -alkylene or -alkenylene bridge,

A⁹ is hydrogen or C₁ -C₄ -alkyl,

A¹⁰ is the radical ##STR4## A¹¹ is the radical ##STR5## A¹² is theradical ##STR6## A¹³ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, CF₃,--CO(C₁ -C₄ -alkyl) or --COO(C₁ -C₄ -alkyl), and G is a C₁ -C₃ -alkylenechain which can be mono- or disubstituted by a substituent from thegroup methyl and phenyl.

The above definition of G embraces methylene, 1,2-ethylene and1,3-propylene, and the groups derived therefrom by substitution of 1 or2 hydrogen atoms by methyl or phenyl, for example: ethylidene,isopropylidene (2,2-propylidene), benzylidene, 1-phenylethylidene,diphenylmethylene, 1,2-propylene, 2,3-butylene,1,1-dimethyl-1,2-ethylene, 1,1-diphenyl-1,2-ethylene,1,2-diphenyl-1,2-ethylene, 1-methyl-1-phenyl-1,2-ethylene, 1,2-butylene,1,3-butylene, 2,2-dimethyl-1,3-propylene,1-methyl-1-phenyl-1,3-propylene, 1,2-diphenyl-1,3-propylene and1,3-diphenyl-1,3-propylene.

When the alkanecarboxylic acid radical Z contains an asymmetricallysubstituted carbon atom (for example --CH(CH₃)Z¹), there can exist twoenantiomeric forms. The invention relates to both the racemates and theR- and S-enantiomers.

The 3-fluoropyridyl-2-oxy-phenoxy derivatives according to the inventionare characterised by a good action against mono- and some dicotyledonousweeds; they are above all effective in the post-emergence processagainst undesirable weeds and wild grasses occurring in cultivatedcrops, such as crops of cereals, maize, rice, soya bean and sugar beet.A particularly valuable aspect is that it is possible with the novelderivatives to combat wild grasses which are otherwise very difficult tocontrol, for example Avena fatua, Avena sterilis, Alopecurusmyosuroides, Lolium perenne, Phalaris sp., Bromus tectorum and variousspecies of Setaria and Panicum. The action under field conditions isachieved even with small applied amounts of less than 1 kg per hectare,at which levels the cultivated crops are not harmed, or are harmed toonly a negligible extent.

Halopyridyloxy-α-phenoxy-propionic acid derivatives have been describedin numerous publications (cp. for example the GermanOffenlegungsschriften Nos. 2,546,251, 2,649,706, 2,714,622 and2,715,284, and the European Publications Nos. 483 and 1473). In thesepublications, the 3-fluoropyridyl-2-oxy-phenoxy derivatives according tothe present invention have in part been taken into account andconcomitantly included in the scope. Compounds of this type have neverhowever been produced or tested. They are distinguished from the knownhalopyridyloxy-α-phenoxypropionic acids by a stronger action, and henceby the fact that it is possible to use them effectively in smalleramounts. Where the applied amount is sufficiently great however, therealso occurs a total-herbicidal action. The novel compounds according tothe invention can be applied both in the pre-emergence process and inthe post-emergence process. The amounts applied can vary within widelimits, for example between 0.05 and 5 kg of active substance perhectare.

Furthermore, the compounds of the formula I have favourablegrowth-regulating effects (growth inhibition). They inhibit inparticular the growth of grasses.

3-Fluoropyridyl-2-oxy-phenoxy derivatives of the formula I which haveproved very active are those which correspond to the formula Ia ##STR7##wherein R¹, R², R⁷, R⁸ and X have the meanings defined under the formulaI, and R¹⁷ is hydrogen, C₁ -C₂ -alkyl or methoxymethyl; and particularlythose compounds in which R¹ and R² are hydrogen or methyl, R¹⁷ is methyland X is chlorine or trifluoromethyl: more especially theα-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionic acidbenzoylmethyl ester and theα-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionicacid-1-benzoylethyl ester.

Also the 3-fluoropyridyl-2-oxy-phenoxy derivatives of the formula Ib##STR8## wherein X, G, R¹⁴, R¹⁵ and p have the meanings defined underthe formula I, and R¹⁷ is hydrogen, C₁ -C₂ -alkyl or methoxymethyl; andparticularly those compounds in which X is chlorine or trifluoromethyl,G is C₁ -C₃ -alkylene, R¹⁴ and R¹⁵ are each methyl or ethyl, and R¹⁷ ismethyl.

Examples of these compounds are:

(2-[4-(5-chloro-3-fluoropyridinyl-2-oxy)-phenoxy]-propionyloxy)-methylphosphonicacid diethyl ester, and

(2-[4-(5-chloro-3-fluoropyridinyl-2-oxy)-phenoxyl]-propionyloxy)-methylphosphonicacid dimethyl ester.

In addition, compounds shown to be active are those of the formula Ic##STR9## wherein X, A¹, A² and R¹⁷ have the meanings defined in theforegoing; and especially those compounds in which X is chlorine ortrifluoromethyl, A¹ is hydrogen, C₁ -C₃ -alkyl, C₃ -C₄ -alkylene or C₃-C₄ -haloalkylene, A² is hydrogen or methyl, and R¹⁷ is methyl: inparticular 4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxyacetic acidmethoxyamide andα-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionic acidmethoxyamide.

Further compounds which have proved interesting are those of the formulaId ##STR10## wherein X, A³, A⁴ and R¹⁷ have the meanings defined in theforegoing; and especially those compounds in which X is chlorine ortrifluoromethyl, A³ and A⁴ together form a C₂ -C₃ -alkylene bridge andR¹⁷ methyl: in particularα-[4-(3-fluoro-5-chloropyridyl-2-oxy)-phenoxy]-propionicacid-(2-oxo-tetrahydrofurfuryl-3-yl) ester; and those compounds of theformula Ie ##STR11## wherein X, A⁷, A⁸, A⁹ and R¹⁷ have the meaningsdefined in the foregoing; especially those compounds in which X ischlorine or trifluoromethyl, A⁷ and A⁸ together form a C₃ -C₅ -alkylenebridge, A⁹ is hydrogen and R¹⁷ is methyl: in particular theα-[4-(3-fluoro-5-chloropyridyl-2-oxy)phenoxy]-propionicacid-(5,5-dimethyl-3-oxo-cyclohex-1-en-1-yl) ester.

Of particular interest also are compounds of the formula If ##STR12##wherein X, G, R₁₂, R¹³ and R¹⁷ have the meanings defined in theforegoing; more especially those compounds in which X is chlorine ortrifluoromethyl, G is C₁ --C₃ -alkylene, and R¹², R¹³ and R¹⁷ are eachmethyl.

Examples of these compounds are:

α-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionicacid-trimethylsilyl-methyl ester,

α-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionicacid-2'-trimethylsilyl-eth-1'-yl ester,

α-[4-(3-fluoro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionicacid-2'-trimethylsilyl-eth-1'-yl ester, and

α-[4-(3-fluoro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionicacid-trimethylsilyl-methyl ester.

Likewise shown to be active are the compounds of the formula Ig##STR13## wherein X and X' are chlorine or trifluoromethyl, and R¹⁷, A⁹and G have the meanings defined in the foregoing; more especiallyhowever those compounds in which G is C₂ -C₄ -alkylene, and R¹⁷ and A⁹are methyl: in particularbis-α-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionic acid glycolester, andbis-α-[4-(3-fluoro-5-trifluoromethyl-pyridyl-2-oxy)-phenoxy]-propionicacid glycol ester.

Also the 3-fluoropyridyl-2-oxy-phenoxy derivatives of the formula Ih##STR14## wherein X, G, R⁷ and A¹³ have the meanings defined under theformula I, and R¹⁷ is hydrogen, C₁ -C₂ -alkyl or methoxymethyl;especially those compounds in which X is chlorine or trifluoromethyl, Gis C₁ -C₃ -alkylene, R⁷ is hydrogen, halogen or methyl, A¹³ is halogenand R¹⁷ is methyl: in particular theα-[4-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionicacid-4'-chlorobenzyl ester.

In addition, the 3-fluoropyridyl-2-oxy-phenoxy derivatives of theformula Ii ##STR15## wherein X, G, R⁷, R⁸ and R⁹ have the meaningsdefined under the formula I, and R¹⁷ is hydrogen, C₁ -C₂ -alkyl ormethoxymethyl; especially those compounds in which X is chlorine ortrifluoromethyl, G is C₁ -C₄ -alkylene, R⁷ and R⁸ are hydrogen, halogen,methyl or CF₃, A⁹ is hydrogen or methyl, and R¹⁷ is methyl, inparticular the 1-(2'-(5-chloro-3-fluoropyridyl-2-oxy)-phenoxy]-propionicacid)-2-(4-chlorophenoxyacetic acid)-glycol ester.

The novel compounds of the formula I are produced by methods known perse.

The first of these processes comprises reacting a 2,3-difluoropyridineof the formula II ##STR16## wherein X has the meaning defined under theformula I, in an inert solvent or diluent and in the presence of theequimolar amount of a base, with a 4-hydroxyphenoxy-α-alkanoic acidderivative of the formula III ##STR17## wherein Z has the meaningdefined under the formula I.

Another process comprises reacting a 4-(3-fluoropyridyl-2-oxy)-phenol ofthe formula IV ##STR18## wherein X has the meaning defined under theformula I, in an inert solvent or diluent and in the presence of theequimolar amount of a base, with a halide of the formula V

    Hal-Z (V)

wherein Hal is chlorine or bromine, and Z has the meaning defined underthe formula I.

A further process comprises converting a 3-aminopyridyl-2-oxyphenoxyderivative of the formula VI ##STR19## wherein X and Z have the meaningsdefined under the formula I, using known methods, into a diazonium salt,and converting this further into the fluorine compound.

Finally, a process for producing the compounds of the formula Icomprises reacting an acid halide of the formula VII ##STR20## whereinHal' is fluorine, chlorine or bromine, and X and R¹⁷ have the meaningsdefined in the foregoing, in an inert solvent or diluent and in thepresence of an equimolar amount of a base, with an alcohol, thiol oramine. By alcohol is meant, inter alia, the classes of compounds HQR andHQ-G-PO(OR¹⁴)(O)_(p) (R¹⁵); and by amine is meant, inter alia, theclasses of compounds such as HNA¹ A² or HNA¹ (OA²).

Some of these reactions are advantageously performed in an organicsolvent or diluent inert to the reactants, for example in an alcohol,ester, ether or ketone, or in dimethylformamide, dimethyl sulfoxide oracetonitrile, or in an aromatic compound, such as benzyl, toluene, andso forth.

The reaction temperatures are between -10° and +150° C., in practicehowever between room temperature and the boiling point of the solvent.Depending on the chosen starting material, the solvent and thetemperature, the reaction time is between one hour up to about one day.

Where a halogen atom is detached in the reaction, the equimolar amountof an acid-binding agent should be used. Suitable as such is essentiallyany inorganic or organic base, for example: NaOH, KOH, NaHCO₃, K₂ CO₃ orK-tertbutylate, and amines, such as trimethylamine, triethylamine,pyridine, 4-dimethylaminopyridine, and so forth.

The novel active substances of the formula I are stable compounds whichare soluble in customary organic solvents, such as alcohols, ethers,ketones, dimethylformamide, dimethyl sulfoxide, and the like. They arenot explosive or corrosive, and the handling of them requires no specialprecautionary measures.

The compounds of the formula I are used either in an unmodified form orpreferably together with auxiliaries customarily employed in formulationpractice, and are thus processed in a known manner for example into theform of emulsion concentrates, directly sprayable or dilutablesolutions, diluted emulsions, wettable powders, soluble powders, dust orgranulates, and also encapsulations in for example polymeric substances.The application processes, such as spraying, atomising, dusting,scattering or pouring, and likewise the type of composition, areselected to suit the objectives to be achieved and the given conditions.

The formulations, that is to say, the compositions or preparationscontaining the active substance of the formula I and optionally a solidor liquid additive, are produced in a known manner, for example by theintimate mixing and/or grinding of the active substances with extenders,such as with solvents, solid carriers and optionally surface-activecompounds (tensides).

Suitable solvents are: aromatic hydrocarbons, preferably the fractionsC₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalicesters, such as dibutyl or dioctylphthalate, aliphatic hydrocarbons,such as cyclohexane or paraffins, alcohols and glycols, as well asethers and esters thereof, such as ethanol, ethylene glycol, ethyleneglycol monomethyl or -ethyl ethers, ketones such as cyclohexanone,strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as optionally epoxidisedvegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders,are as a rule natural mineral fillers, such as calcite, talcum, kaolin,montmorillonite or attapulgite. In order to improve the physicalproperties, it is possible to add highly dispersed silicic acid orhighly dispersed absorbent polymers. Suitable granulated adsorptivecarriers are porous types, for example pumice, ground brick, sepioliteor bentonite; and suitable nonsorbent carriers are materials such ascalcite or sand. There can also be used a great number of pre-granulatedmaterials of inorganic or organic nature, such as in particular dolomiteor ground plant residues.

Suitable surface-active compounds are, depending on the nature of theactive substance of the formula I to be formulated, nonionic, cationicand/or anionic tensides having good emulsifying, dispersing and wettingproperties. By `tensides` are also meant mixtures of tensides.

Suitable anionic tensides are both so-called watersoluble soaps as wellas water-soluble, synthetic, surface-active compounds.

Soaps which are applicable are for example the alkali metal,alkaline-earth metal or optionally substituted ammonium salts of higherfatty acids (C₁₀ -C₂₀), for example the Na or K salts of oleic orstearic acid, or of natural fatty acid mixtures, which can be obtainedfor example from coconut oil or tallow oil. Also to be mentioned are thefatty acid-methyl-taurine salts. So-called synthetic tensides arehowever more frequently used, particularly fatty sulfonates, fattysulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.The fatty sulfonates or sulfates are as a rule in the form of alkalimetal, alkaline-earth metal or optionally substituted ammonium salts,and contain an alkyl group having 8 to 22 C atoms, `alkyl` includingalso the alkyl moiety of acyl groups, for example the Na or Ca salt ofligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcoholsulfate mixture produced from natural fatty acids. Included among theseare also the salts of sulfuric acid esters and sulfonic acids of fattyalcohol ethylene oxide adducts. The sulfonated benzimidazole derivativespreferably contain 2 sulfonic acid groups and a fatty acid group having8-22 C atoms. Alkylarylsulfonates are for example the Na, Ca ortriethanolamine salts of dodecylbenzenesulfonic acid, ofdibutylnaphthalenesulfonic acid or of a naphthalenesulfonicacid-formaldehyde condensation product. Also suitable are correspondingphosphates, for example salts of the phosphoric ester of ap-nonylphenol-(4-14)-ethylene oxide adduct.

Suitable nonionic tensides are in particular polyglycol etherderivatives of aliphatic or cycloaliphatic alcohols, saturated orunsaturated fatty acids and alkylphenols, which can contain 3 to 30glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)hydrocarbon radical and 6 to 18 carbon atoms in the alkyl moiety of thealkylphenols.

Further suitable nonionic tensides are the watersoluble polyethyleneoxide adducts, which contain 20 to 250 ethylene glycol ether groups and10 to 100 propylene glycol ether groups, with polypropylene glycol,ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usuallycontain 1 to 5 ethylene glycol units per propylene glycol unit. Examplesof nonionic tensides which may be mentioned are:nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,polypropylene/polyethyleneoxy adducts, tributylphenoxypolyethoxyethanol,polyethylene glycol and octylphenoxypolyethoxyethanol. Suitable also arefatty acid esters of polyoxyethylenesorbitan, such aspolyoxyethylene-sorbitan-trioleate.

In the case of the cationic tensides, they are in particular quaternaryammonium salts which contain as N-substituents at least one alkyl grouphaving 8 to 22 carbon atoms and, as further substituents, lower,optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. Thesalts are preferably in the form of halides, methyl sulfates or ethylsulfates, for example stearyltrimethylammonium chloride orbenzyldi(2-chloroethyl)ethylammonium bromide.

The tensides customarily used in formulation practice are described,inter alia, in the following publications:

"Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp.,Ridgewood, N.J., 1979;

H. Stache, "Tensid Taschenbuch", 2nd Edition, C. Hanser Verlag, Munichand Vienna, 1981; and

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, ChemicalPublishing Co., New York, 1980-81.

These preparations contain as a rule 0.1 to 99%, particularly 0.1 to95%, of active substance of the formula I, 1 to 99% of a solid or liquidadditive, and 0 to 25%, especially 0.1 to 25%, of a tenside.

Whereas commercial products are preferably in the form of concentratedcompositions, the preparations employed by the end-user are as a rulediluted.

The compositions can also contain further additives, such asstabilisers, antifoaming agents, viscosity regulators, binders andadhesives, and also fertilisers or other active ingredients forobtaining special effects.

The following Examples describe in detail the production of the3-fluoropyridyl-2-oxy-phenoxy derivatives of the formula I according tothe invention, and of compositions containing such compounds as activeingredients. Further esters according to the invention which areobtained in an analogous manner are listed in the Tables following theExamples. Temperatures are given in degrees Centigrade and percentagevalues relate to weight.

EXAMPLE 1

Production of(±)-2-[4-(5-chloro-3-fluoropyridinyl-2-oxyphenoxy]-propionicacid-(2-phenyl-2-oxo-ethyl)ester. ##STR21##

A mixture of 10.68 g (0.032 mol) ofsodium-2-[4-(5-chloro-3-fluoropyridin-2-yloxy)-phenoxy]-propionate and6.1 g (0.032 mol) of phenacyl bromide (98%) in 30 ml ofdimethylformamide is heated for 1 hour at 80° C. The reaction mixture isthen poured into ice/water, and is extracted three times with ethylacetate. The extracts are washed with brine, dried with magnesiumsulfate, filtered, and concentrated by evaporation. The product obtainedis purified in petroleum ether/ether (2:1) through a short silica gelcolumn. After the solvent has been evaporated off, the yield is 12 g ofproduct; n_(D) ³⁵ =1.5679.

EXAMPLE 2

Production of(±)-2-[4-(5-chloro-3-fluoropyridin-2-yloxy)phenoxy]-propionicacid-(2,2-dicyanovinyl) amide. ##STR22##

4.95 g (0.015 mol) of(±)-2-[4-(5-chloro-3-fluoropyridinyl-2-oxy)-phenoxy]-propionic acidchloride and 1.5 g (0.0155 mol) of 2,2-dicyanovinylamine are dissolvedin 20 ml of acetonitrile in a sulfonating flask, and the solution iscooled to 5° C. with stirring. There are then added dropwise 2.2 ml(0.015 mol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (97%) dissolved in 5ml of acetonitrile. The mixture is stirred at the same temperature for 1hour, and the temperature is subsequently allowed to rise to 20° C.After 16 hours, the reaction mixture is poured onto ice, and 1 ml (0.015mol) of methanesulfonic acid is added. The mixture is afterwardsextracted twice with ethyl acetate; the extracts are then washed withbrine, dried with magnesium sulfate, filtered, and concentrated byevaporation. The crude product is purified in ethyl acetate/hexane (1:1)through a short silica gel column to thus obtain, after removal of thesolvent by evaporation, 5.0 g (86%) of the title product; m.p. 129°-131°C.

EXAMPLE 3

Production of(±)-2-[4-(5-chloro-3-fluoropyridinyl-2-oxy)phenoxy]-propionic acidmethoxyamide. ##STR23##

1.7 g (0.02 mol) of O-methyl-hydroxylamine hydrochloride, 5.6 ml (0.04mol) of triethylamine and 30 ml of toluene are cooled with stirring in asulfonating flask to 5° C., and there are then added dropwise 4.95 g(0.015 mol) of(±)-2-[4-(5-chloro-3-fluoropyridinyl-2-oxy)-phenoxy]-propionic acidchloride in 15 ml of toluene. The reaction mixture is subsequentlystirred for a further 3 hours at room temperature; it is afterwardspoured into ice/water, and extracted three times with ethyl acetate. Theextracts are washed with brine, dried with magnesium sulfate, filtered,and concentrated by evaporation. The yield is thus 3.9 g of an oil whichcrystallises on being stirred up in ether; m.p. 103°-105° C.

EXAMPLE 4

Production of2-[4-(3-fluoro-3-trifluoromethylpyridyl-2-oxy)phenoxy]-propionicacid-[2-(0,0-dimethylphosphonyl)ethyl] ester. ##STR24##

7.7 g (0.05 mol) of 2-hydroxyethyl-0,0-dimethylphosphonate are placedtogether with 6.9 ml (0.05 mol) of triethylamine and a spatula-tip of4-piperadinopyridine into 130 ml of ethyl acetate. There are then addeddropwise at room temperature, with stirring, 17.9 g (0.05 mol) of2-[4-(3-fluoro-5-trifluoromethylpyridyl-2-oxy)-phenoxy]-propionic acidchloride in 20 ml of ethyl acetate. The reaction mixture is stirred for1 hour at 30°-35° C. and for 1 hour under refluxing conditions; themixture is subsequently allowed to cool and is then filtered; thefiltrate is afterwards treated with active charcoal, dried over sodiumsulfate and concentrated by evaporation to thus obtain 22.1 g of a brownoil, which is finally chromatographed with CH₂ Cl₂ /CH₃ OH (95.5)through silica gel; yield 17.5 g of a light-yellow oil, n_(D) ³⁰=1.4973.

The following compounds are produced in a manner analogous to that ofthe above Examples.

                                      TABLE 1                                     __________________________________________________________________________     ##STR25##                                                                    No. X   R.sup.17                                                                          Q  R.sup.1                                                                           R.sup.2                                                                           R.sup.8                                                                            R.sup.7                                                                           Physical properties                           __________________________________________________________________________    1.01                                                                              Cl  CH.sub.3                                                                          O  H   H   H    H   n.sub.D.sup.35 1.5679                         1.02                                                                              Cl  H   O  H   H   H    H                                                 1.03                                                                              Cl  C.sub.2 H.sub.5                                                                   O  H   H   H    H                                                 1.04                                                                              CF.sub.3                                                                          C.sub.2 H.sub.5                                                                   O  H   H   H    H                                                 1.05                                                                              CF.sub.3                                                                          CH.sub.3                                                                          O  H   H   H    H                                                 1.06                                                                              CF.sub.3                                                                          H   O  H   H   H    H                                                 1.07                                                                              Cl  CH.sub.3                                                                          O  H   CH.sub.3                                                                          H    H   n.sub.D.sup.35 1.5631                         1.08                                                                              Cl  CH.sub.3                                                                          O  H   H   4-Cl H                                                 1.09                                                                              Cl  CH.sub.3                                                                          O  H   H   2-Cl 6-Cl                                              1.10                                                                              Cl  CH.sub.3                                                                          O  H   H   2-Cl H                                                 1.11                                                                              Cl  CH.sub.3                                                                          O  H   H   2-OCH.sub.3                                                                        H                                                 1.12                                                                              Cl  CH.sub.3                                                                          O  H   CH.sub.3                                                                          2-Cl H                                                 1.13                                                                              Cl  CH.sub.3                                                                          O  H   CH.sub.3                                                                          4-CH.sub.3                                                                         H                                                 1.14                                                                              Cl  CH.sub.3                                                                          O  CH.sub.3                                                                          CH.sub.3                                                                          H    H                                                 __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR26##                                                                    No. X    R.sup.17                                                                          Z.sup.1        Physical properties                               __________________________________________________________________________    2.01                                                                              Cl   H   CONH.sub.2                                                       2.02                                                                              Cl   CH.sub.3                                                                          CONH.sub.2     m.p. 162-164° C.                           2.03                                                                              Cl   H   CONHOCH.sub.3                                                    2.04                                                                              Cl   CH.sub.3                                                                          CONHOCH.sub.3  m.p. 103-104° C.                           2.05                                                                              Cl   CH.sub.3                                                                          CON(CH.sub.3)OCH.sub.3                                                                       resinous oil                                      2.06                                                                              Cl   CH.sub.3                                                                          CONHOC.sub.2 H.sub.5                                                                         m.p. 78° C.                                2.07                                                                              Cl   CH.sub.3                                                                          CONHCH.sub.3   m.p. 145-147° C.                           2.08                                                                              Cl   CH.sub.3                                                                          CON(CH.sub.3)CH.sub.3                                            2.09                                                                              Cl   CH.sub.3                                                                          CONHOCH.sub.2 CHCH.sub.2                                                                     m.p. 82-84° C.                             2.10                                                                              Cl   CH.sub.3                                                                          CONHCHC(CN).sub.2                                                                            m.p. 129-131° C.                           2.11                                                                              Br   CH.sub.3                                                                          CONHOCH.sub.3                                                    2.12                                                                              Br   CH.sub.3                                                                          CONHCHC(CN).sub.2                                                2.13                                                                              CF.sub.3                                                                           CH.sub.3                                                                          CONHOCH.sub.3  m.p. 64° C.                                2.14                                                                              CF.sub.3                                                                           CH.sub.3                                                                          CON(CH.sub.3)OCH.sub.3                                           2.15                                                                              CF.sub.3                                                                           CH.sub.3                                                                          CONHCHC(CN).sub.2                                                2.16                                                                              Cl   CH.sub.3                                                                          1,2-oxazolidinyl-2-                                                           carbonyl                                                         2.17                                                                              CF.sub.3                                                                           CH.sub.3                                                                          1,2-oxazolidinyl-2-                                                           carbonyl                                                         2.18                                                                              Cl   CH.sub.3                                                                          CSOCH.sub.3                                                      2.19                                                                              Cl   CH.sub.3                                                                          C(OCH.sub.2 SCH.sub.3)NC.sub.6 H.sub.5                           2.20                                                                              Cl   CH.sub.3                                                                          1,3-oxazolin-2-yl                                                2.21                                                                              Cl   CH.sub.3                                                                          4-methyl-1,3-oxa-                                                             zolin-2-yl                                                       2.22                                                                              CF.sub.3                                                                           CF.sub.3                                                                          CONHOC.sub.2 H.sub.5                                                                         m.p. 89° C.                                2.23                                                                              Cl   CH.sub.3                                                                          CONHOCH.sub.2 CHCHCl                                                                         m.p. 109-110° C.                           2.24                                                                              Cl   CH.sub.3                                                                          CONHOCH.sub.2C(CH.sub.3)CH.sub.2                                                             m.p. 85-86° C.                             2.25                                                                              Cl   CH.sub.3                                                                          CONHC.sub.2 H.sub.5                                                                          m.p. 105-107° C.                           __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR27##                                                                    No.                                                                              X  R.sup.17                                                                         Z.sup.1             Physical properties                              __________________________________________________________________________    3.01                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2                             3.02                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 P(O)(OCH.sub.3).sub.2                                                                 n.sub.D.sup.30 1.5317                            3.03                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 CH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2                    3.04                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 CH.sub.2 P(O)(OCH.sub.3).sub.2                           3.05                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 CH.sub.2 CH.sub.2 P(O)(OC.sub.2 H.sub.5).sub.2           3.06                                                                             Cl CH.sub.3                                                                         COOCH.sub.2CH(CH.sub.3)P(O)(OC.sub.5 H.sub.2).sub.2                  3.07                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 P(O)(OCH.sub.3).sub.2                                    3.08                                                                             Cl H  COOCH.sub.2 P(O)(OCH.sub.3).sub.2                                    3.09                                                                             Cl CH.sub.3                                                                         COOCH(CH.sub.3)P(O)(OCH.sub.3).sub.2                                 3.10                                                                             Cl CH.sub.3                                                                         COOC(CH.sub.3).sub.2 P(O)(OCH.sub.3).sub.2                           3.11                                                                             Cl CH.sub.3                                                                         COOCH.sub.2 P(O)(OCH.sub.3)CH.sub.3                                  3.12                                                                             CF.sub.3                                                                         CH.sub.3                                                                         COOCH.sub.2 P(O)(OC.sub.2 H.sub.5)CH.sub.3                                                        n.sub.D.sup.30 1.4992                            3.13                                                                             Cl CH.sub.3                                                                         COOCH(CH.sub.3)P(O)(OCH.sub.3)CH.sub.3                               3.14                                                                             Cl CH.sub.3                                                                         COOCH(CH.sub.3)P(O)(OC.sub.2 H.sub.5).sub.2                                                       n.sub.n.sup.30 1.5140                            3.15                                                                             CF.sub.3                                                                         CH.sub.3                                                                         COOCH.sub.2 P(O)(OCH.sub.3).sub.2                                    3.16                                                                             CF.sub.3                                                                         CH.sub.3                                                                         COOCH.sub.2 CH.sub.2 P(O)(OCH.sub.3).sub.2                                                        n.sub.D.sup.30 1.4973                            __________________________________________________________________________

                  TABLE 4                                                         ______________________________________                                         ##STR28##                                                                                                       Physical                                   No.  X      R.sup.17                                                                             Z.sup.1         properties                                 ______________________________________                                        4.01 Cl     CH.sub.3                                                                             4,4-dimethyl-6-oxo-cyclo-                                                                     m.p. 83-85° C.                                         hex-1-en-2-ol-1-ylcarbonyl                                 4.02 Cl     CH.sub.3                                                                             5,5-dimethyl-3-oxo-cyclo-                                                                     oil                                                           hex-1-en-1-yloxycarbonyl                                   4.03 Cl     CH.sub.3                                                                             morpholinoethoxycarbonyl                                                                      n.sub.D.sup.30 1.5378                      4.04 Cl     CH.sub.3                                                                             2-oxo-tetrahydrofuryl-                                                        3-oxy-carbonyl                                             4.05 Cl     CH.sub.3                                                                             isoxazolidin-2-yl-carbonyl                                 4.06 CF.sub.3                                                                             CH.sub.3                                                                             isoxazolidin-2-yl-carbonyl                                 4.07 Cl     CH.sub.3                                                                             3-methyl-isoxazolidin-2-yl-                                                   carbonyl                                                   4.08 CF.sub.3                                                                             CH.sub.3                                                                             3-methyl-isoxazolidin-2-yl-                                                   carbonyl                                                   4.09 Cl     CH.sub.3                                                                             5-methyl-isoxazolidin-2-yl-                                                   carbonyl                                                   4.10 CF.sub.3                                                                             CH.sub.3                                                                             5-methyl-isoxazolidin-2-yl-                                                   carbonyl                                                   ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                         ##STR29##                                                                                                   Physical                                       No.  X      Z                  properties                                     ______________________________________                                        5.01 Cl     CH.sub.2 COOCH.sub.3                                                                             m.p. 81-82° C.                          5.02 CF.sub.3                                                                             CH.sub.2 COOCH.sub.3                                              5.03 Br     CH.sub.2 COOCH.sub.3                                              5.04 Cl     CH(C.sub.2 H.sub.5)COOCH.sub.3                                    5.05 CF.sub.3                                                                             CH(C.sub.2 H.sub.5)COOCH.sub.3                                    5.06 Cl     CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                 5.07 CF.sub.3                                                                             CH(CH.sub.2 OCH.sub.3)COOCH.sub.3                                 5.08 Cl     CH.sub.2 COOCH.sub.2 CCH                                          5.09 CF.sub.3                                                                             CH.sub.2 COOCH.sub.2 CCH                                          5.10 Cl     CH.sub.2 COOCH(CH.sub.3)COOC.sub.2 H.sub.5                        5.11 CF.sub.3                                                                             CH.sub.2 COOCH(CH.sub.3)COOC.sub.2 H.sub.5                        5.12 Cl     CH.sub.2 COSCH.sub.2 COOCH.sub.3                                  5.13 CF.sub.3                                                                             CH.sub.2 COSCH.sub.2 COOCH.sub. 3                                 5.14 Cl     CH.sub.2 C(CN)CH.sub.2                                            5.15 Cl     CH.sub.2C(COOCH.sub.3)CH.sub.2                                    5.16 CF.sub.3                                                                             CH.sub.2 C(COOCH.sub.3)CH.sub.2                                   5.17 Cl     CH.sub.2 C(COOC.sub.2 H.sub.5)CH.sub.2                                                           m.p. 68° C.                             5.18 Cl     CH(CH.sub.3)COO(4-chlorobenzyl)                                                                  n.sub.D.sup.30 1.5721-   (racemate)            5.19 Cl     CH(CH.sub.3)COO(4-chlorobenzyl)                                                                  m.p. 58-60° C. (2R)                     5.20 Cl     CH(CH.sub.3)COO(4-chlorobenzyl)                                                                  m.p. 63-64° C. (2S)                     5.21 CF.sub.3                                                                             CH(CH.sub.3)COO(4-chlorobenzyl)                                   5.22 Cl     CH(CH.sub.3)COO(2-chlorobenzyl)                                   ______________________________________                                    

                                      TABLE 6                                     __________________________________________________________________________     ##STR30##                                                                                                 Physical                                         No.                                                                              X  G          R.sup.12                                                                         Observations                                                                           properties                                       __________________________________________________________________________    6.01                                                                             Cl CH.sub.2CH.sub.2                                                                         CH.sub.3                                                                         2Renantiomer                                                                           n.sub.D.sup.35 1.5181                                                         [α].sub.D.sup.20 = +37.0°                                        (acetone)                                        6.02                                                                             Cl CH.sub.2   CH.sub.3                                                                         2Renantiomer                                                                           n.sub.D.sup.35 1.5201                                                         [α].sub.D.sup.20 = +41.3°                                        (acetone)                                        6.03                                                                             CF.sub.3                                                                         CH.sub.2   CH.sub.3                                                                         racemate m.p. 61-63° C.                            6.04                                                                             CF.sub.3                                                                         CH.sub.2CH.sub.2                                                                         CH.sub.3                                                                         racemate n.sub.D.sup.35 1.4842                            6.05                                                                             Cl CH.sub.2CH.sub.2                                                                         CH.sub.3                                                                         racemate n.sub.D.sup.35  1.5201                           6.06                                                                             Cl CH.sub.2   CH.sub.3                                                                         racemate n.sub.D.sup.35 1.5155                            6.07                                                                             Cl CH.sub.2   C.sub.2 H.sub.5                                              6.08                                                                             Cl CH.sub.2CH.sub.2                                                                         C.sub.2 H.sub.5                                              6.09                                                                             Cl CH(CH.sub.3)CH.sub.2                                                                     CH.sub.3                                                     6.10                                                                             Cl CH.sub.2 CH(CH.sub.3)                                                                    CH.sub.3                                                     6.11                                                                             Cl CH(CH.sub.3)                                                                             CH.sub.3                                                     6.12                                                                             CF.sub.3                                                                         CH(CH.sub.3)                                                                             CH.sub.3                                                     __________________________________________________________________________

                                      TABLE 7                                     __________________________________________________________________________     ##STR31##                                                                    No.  X    G          A.sup.9                                                                            R.sup.7                                                                             R.sup.8                                                                              Physical properties                    __________________________________________________________________________    7.01 Cl   CH.sub.2CH.sub.2                                                                         H    4-Cl  H      n.sub.D.sup.35 1,5547                  7.02 Cl   CH.sub.2CH.sub.2                                                                         H    4-Cl  2-Cl                                          7.03 Cl   CH.sub.2CH.sub.2                                                                         CH.sub.3                                                                           4-Cl  H                                             7.04 Cl   (CH.sub.2).sub.3                                                                         H    4-Cl  H                                             7.05 Cl   CH.sub.2CH.sub.2                                                                         CH.sub.3                                                                           4-Cl  2-Cl                                          7.06 Cl   CH.sub.2CH.sub.2                                                                         H    4-Cl  2-CH.sub.3                                    7.07 CF.sub.3                                                                           CH.sub.2 CH.sub.2                                                                        H    4-Cl  H                                             7.08 CF.sub.3                                                                           CH.sub.2 CH.sub.2                                                                        H    4-Cl  2-Cl                                          7.09 CF.sub.3                                                                           CH.sub.2 CH.sub.2                                                                        CH.sub.3                                                                           4-Cl  H                                             7.10 CF.sub.3                                                                           (CH.sub.2).sub.3                                                                         H    4-Cl  H                                             __________________________________________________________________________

                                      TABLE 8                                     __________________________________________________________________________     ##STR32##                                                                    No.       X     X'    R.sup.17                                                                            A.sup.9                                                                             G            Physical                       __________________________________________________________________________                                                   properties                     8.01      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                            CH.sub.2CH.sub.2                                                                           n.sub.D.sup.35 1.5587          8.02      Cl    Cl    CH.sub.3                                                                            H     CH.sub.2CH.sub.2                            8.03      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                            (CH.sub.2).sub.3                            8.04      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2                        8.05      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                            (CH.sub. 2).sub.4                           8.06      Cl    Cl    CH.sub.3                                                                            CH.sub.3                                                                            CH(CH.sub.3)CH(CH.sub.3)                    8.07      CF.sub.3                                                                            CF.sub.3                                                                            CH.sub.3                                                                            CH.sub.3                                                                            CH.sub.2CH.sub.2                            8.08      CF.sub.3                                                                            CF.sub.3                                                                            CH.sub.3                                                                            H     CH.sub.2CH.sub.2                            8.09      CF.sub.3                                                                            CF.sub.3                                                                            CH.sub.3                                                                            CH.sub.3                                                                            (CH.sub.2).sub.3                            8.10      CF.sub.3                                                                            CF.sub.3                                                                            CH.sub.3                                                                            CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2                        8.11      CF.sub.3                                                                            CF.sub.3                                                                            CH.sub.3                                                                            CH.sub.3                                                                            (CH.sub.2).sub.4                            8.12      CF.sub.3                                                                            Cl    CH.sub.3                                                                            CH.sub.3                                                                            CH.sub.2 CH.sub.2                           8.13      CF.sub.3                                                                            Cl    CH.sub.3                                                                            CH.sub.3                                                                            CH(CH.sub.3)CH.sub.2                        __________________________________________________________________________

EXAMPLE 5

Production of a formulation with liquid active ingredients of theformula I (%=percent by weight)

    ______________________________________                                        Emulsion concentrates                                                                            (a)       (b)    (c)                                       ______________________________________                                        2-[4-(5-chloro-3-fluoropyridyl-                                                                  20%       40%    50%                                       2'-oxy)-phenoxy]-propionic                                                    acid methoxyamide                                                             calcium dodecylbenzenesulfonate                                                                   5%        8%    5.8%                                      castor oil-polyethylene glycol                                                                    5%       --     --                                        ether (36 mols of ethylene oxide                                              tributylphenol-polyethylene glycol                                                               --        12%    4.2%                                      (30 mols of ethylene oxide)                                                   cyclohexanone      --        15%    20%                                       xylene mixture     70%       25%    20%                                       ______________________________________                                    

Emulsions of any required concentration can be produced fromconcentrates of this type of dilution with water.

    ______________________________________                                        Solutions          (a)    (b)     (c)  (d)                                    ______________________________________                                        active ingredient according                                                                      80%    10%     5%   95%                                    to Tables 1-8                                                                 ethylene glycol-monomethyl ether                                                                 20%    --      --   --                                     polyethylene glycol (M.W. 400)                                                                   --     70%     --   --                                     N--methyl-2-pyrrolidone                                                                          --     20%     --   --                                     epoxidised coconut oil                                                                           --     --       1%   5%                                    ligroin (boiling limits 160-190° C.)                                                      --     --      94%  --                                     ______________________________________                                    

The solutions are suitable for application in the form of very finedrops.

    ______________________________________                                        Granulates           (a)    (b)                                               ______________________________________                                        active ingredient according                                                                        5%     10%                                               to Tables 1-8                                                                 kaolin               94%    --                                                highly dispersed silicic acid                                                                      1%     --                                                attapulgite          --     90%                                               ______________________________________                                    

The active ingredient is dissolved in methylene chloride; the solutionis subsequently sprayed onto the carrier, and the solvent is evaporatedoff in vacuo.

    ______________________________________                                        Dusts               (a)     (b)                                               ______________________________________                                        active ingredient from                                                                            2%      5%                                                Tables 1-8                                                                    highly dispersed silicic acid                                                                     1%      5%                                                talcum              97%     --                                                kaolin              --      90%                                               ______________________________________                                    

Dusts ready for use are obtained by the intimate mixing together of thecarriers with the active ingredient.

Formulation Examples for solid active ingredients of the formula I(%=percent by weight)

    ______________________________________                                        Wettable powders       (a)     (b)                                            ______________________________________                                        active ingredient from 20%     60%                                            Tables 1-8                                                                    sodium lignin sulfonate                                                                              5%      5%                                             sodium lauryl sulfate  3%      --                                             sodium diisobutylnaphthalene sulfonate                                                               --      6%                                             octylphenolpolyethylene glycol ether                                                                 --      2%                                             (7-8 mols of ethylene oxide)                                                  highly dispersed silicic acid                                                                        5%      27%                                            kaolin                 67%     --                                             ______________________________________                                    

The active ingredient is well mixed with the additives and the mixtureis thoroughly ground in a suitable mill. Wettable powders which can bediluted with water to give suspensions of the required concentration areobtained.

    ______________________________________                                        Emulsion concentrate                                                          ______________________________________                                        active ingredient from 10%                                                    Tables 1-8                                                                    octylphenol polyethylene glycol ether                                                                 3%                                                    (4-5 mols of ethylene oxide)                                                  calcium dodecylbenzenesulfonate                                                                       3%                                                    castor oil polyglycol ether                                                                           4%                                                    (36 mols of ethylene oxide)                                                   cyclohexanone          30%                                                    xylene mixture         50%                                                    ______________________________________                                    

Emulsions of the concentration required can be obtained from thisconcentrate by dilution with water.

    ______________________________________                                        Dusts               (a)    (b)                                                ______________________________________                                        active ingredient from                                                                             5%     8%                                                Tables 1-8                                                                    talcum              95%    --                                                 kaolin              --     92%                                                ______________________________________                                    

Dusts ready for use are obtained by mixing the active ingredient withthe carriers and grinding the mixture in a suitable mill.

    ______________________________________                                        Extruder granulate                                                            ______________________________________                                        active ingredient from                                                                           10%                                                        Tables 1-8                                                                    sodium lignin sulfonate                                                                           2%                                                        carboxymethylcellulose                                                                            1%                                                        kaolin             87%                                                        ______________________________________                                    

The active ingredient is mixed and ground with the additives, and themixture is moistened with water. This mixture is extruded and then driedin a stream of air.

    ______________________________________                                        Coated granulate                                                              ______________________________________                                        active ingredient from                                                                              3%                                                      Tables 1-8                                                                    polyethylene glycol (M.W. 200)                                                                      3%                                                      kaolin                94%                                                     ______________________________________                                    

The finely ground active ingredient is evenly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Dustfree coatedgranulates are obtained in this manner.

    ______________________________________                                        Suspension concentrate                                                        ______________________________________                                        active ingredient from 40%                                                    Tables 1-8                                                                    ethylene glycol        10%                                                    nonylphenolpolyethylene glycol ether                                                                  6%                                                    (15 mols of ethylene oxide)                                                   sodium lignin sulfonate                                                                              10%                                                    carboxymethylcellulose  1%                                                    37% aqueous formaldehyde solution                                                                    0.2%                                                   silicone oil in the form of a 75%                                                                    0.8%                                                   aqueous emulsion                                                              water                  32%                                                    ______________________________________                                    

The finely ground active ingredient is intimately mixed with theadditives. There is thus obtained a suspension concentrate from whichcan be produced, by dilution with water, suspensions of theconcentration required.

EXAMPLE 6

Testing of the herbicidal action Pre-emergence herbicidal action(inhibition of germination)

Immediately after sowing of the test plants in pots in a greenhouse, thesurface of the soil is sprayed with an aqueous dispersion of the activeingredient, which has been prepared either from a 25% emulsonconcentrate, or from a 25% wettable powder in the case of activeingredients which cannot be prepared as emulsion concentrates owing toinadequate solubility. Various concentrations are used, and the amountof active ingredient is calculated on the basis of kg per hectare. Thepots are then kept in a greenhouse at 22°-25° C. with 50-70% relativehumidity, and are regularly watered. The test results are evaluatedafter three weeks.

The tested compounds from Tables 1-8 exhibit a good to very goodphytotoxic action against the monocotyledons used in the tests.

Post-emergence herbicidal action (contact herbicide)

A considerable number of weeds and cultivated plants, bothmonocotyledonous and dicotyledonous, are grown in pots in a greenhouse,and after emergence (in the 4- to 6-leaf stage) the plants are sprayedwith an aqueous active-ingredient dispersion in varying dosages,expressed in kg of active ingredient per hectare, and the treated plantsare kept at 24°-26° C. with 45-60% relative humidity. The test resultsare evaluated two weeks after the treatment.

In this case too, the tested compounds from Tables 1-8 have an excellentaction against the monocotyledonous wild grasses used in the tests.

Reduction of growth of grasses

Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina andDactylis glomerata are sown in a soil/ peat/sand mixture (6:3:1) inplastic trays and watered in the usual manner. The emerged grasses arecut back each week to a height of 4 cm, and are sprayed 40 days aftersowing and 1 day after the last cutting with an aqueous spray liquor ofin each case a compound of the formula I. The amount of activeingredient is equivalent to 0.05-2 kg of active ingredient per hectare.The growth of the grasses is compared, 10 and 21 days after application,with that of the untreated control specimens. The tested compounds fromTables 1-8 in an applied amount of 0.05 kg per hectare reduce the growthof the grasses by 18-32%.

What is claimed is:
 1. A 3-fluoropyridyl-2-oxyphenoxy derivative whichcorresponds to the formula Ih ##STR33## wherein X is chlorine ortrifluoromethyl, G is C₁ -C₃ -alkylene, R⁷ is hydrogen, halogen ormethyl, A¹³ is halogen and R¹⁷ is methyl. 2.2-[4-(5-Chloro-3-fluoropyridyl-2-oxy)-phenoxy]propionicacid-4'-chlorobenzyl ester according to claim
 1. 3.(2R)-2-[4-(5-Chloro-3-fluoropyridyl-2-oxy)-phenoxy]propionicacid-4'-chlorobenzyl ester according to claim
 1. 4. A herbicidal andplant-growth regulating composition comprising, as active ingredient, aherbicidally and plant-growth regulatingly effective amount of a3-fluoropyridyl-2-oxyphenoxy derivative according to claim 1, togetherwith inert carrier material.
 5. A method of selectively controllinggramineous weeds, which method comprises applying thereto or to thelocus thereof a herbicidally effective amount of a3-fluoropyridyl-2-oxy-phenoxy derivative, according to claim
 1. 6. Amethod of reducing the growth of plants, in particular the growth ofgrasses, which method comprises applying thereto or to the locus thereofa herbicidally effective amount of a 3-fluoropyridyl-2-oxy-phenoxyderivative of the formula Ih according to claim 1.